CN103842405B - Polycarbonate and preparation method thereof - Google Patents
Polycarbonate and preparation method thereof Download PDFInfo
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
- C08K5/41—Compounds containing sulfur bound to oxygen
- C08K5/42—Sulfonic acids; Derivatives thereof
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/04—Aromatic polycarbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/16—Aliphatic-aromatic or araliphatic polycarbonates
- C08G64/1608—Aliphatic-aromatic or araliphatic polycarbonates saturated
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G64/00—Macromolecular compounds obtained by reactions forming a carbonic ester link in the main chain of the macromolecule
- C08G64/20—General preparatory processes
- C08G64/30—General preparatory processes using carbonates
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
Abstract
The feature of polycarbonate resin of the present invention is the repeating unit comprising formula 1, formula 2 and formula 3.
Description
Technical field
The present invention relates to polycarbonate and preparation method thereof.More particularly, the present invention relates to the polycarbonate with excellent chemical resistant properties and shock resistance and preparation method thereof.
Background technology
Polycarbonate is the thermoplastic material having about 135 DEG C or higher heat deflection temperature (HDT) and can show excellent mechanical property, dimensional stability, thermotolerance and the transparency comprising shock resistance and excellent self-extinguishing.Polycarbonate resin is widely used in various application, such as, in the outer material, trolley part etc. of electronics and electric product.
But although have the excellent transparency and mechanical property, polycarbonate is for having restriction in outer material.When plastic material is used as outer material, often this product of coating is to strengthen its aesthetic property.In this case, can be dried with the application of various organic solvent diluting in the surface of molded resin.Organic solvent as thinner can infiltrate in polycarbonate, and this can reduce the transparency and physical strength.Therefore, in order in the process used polycarbonate is used in often be exposed to various organic solvent product in, the patience had for these organic solvents for polycarbonate is important.Propose various method to improve the chemical resistant properties of polycarbonate resin.
Korean Patent disclose No. 2007-0071446, Korean Patent disclose No. 2009-0026359 and Korean Patent disclose No. 2010-0022376 disclose by with the chemical-resistant method there are other mixed with resin of chemical-resistant improving polycarbonate resin.But although these methods can improve chemical resistant properties a little, they can reduce shock resistance.In order to improve the shock resistance causing due to mixing reducing, impact modifier can be used.But impact modifier obviously can reduce the transparency of resin.
JP05-339390 and No. the 5th, 401,826, United States Patent (USP) disclose and improve chemical-resistant method by preparation copolymerization polycarbonate, wherein introduce having chemical-resistant material in conventional polycarbonate resin.
The example of copolymerization material is to improve chemical-resistant 4,4'-bis-phenol with polycarbonate resin copolymerization.But although 4,4'-bis-phenol can improve chemical resistant properties, it can also reduce shock resistance, thus the advantage of deteriorated polycarbonate.Especially, along with the amount of 4,4'-used bis-phenols increases, mobility sharply declines, thus causes mouldability deterioration.
Summary of the invention
Technical problem
One aspect of the present invention provides polycarbonate with excellent chemical resistant properties and mobility and not deteriorated shock resistance and preparation method thereof.
Another aspect of the present invention provides chemical resistant properties, mobility, room temperature/low temperature impact strength and the thermotolerance with excellence to keep polycarbonate of the transparency and preparation method thereof simultaneously.
The present invention as described below can realize above-mentioned aspect and other aspects.
Technical scheme
One aspect of the present invention relates to a kind of polycarbonate.This polycarbonate comprises the repeating unit represented by formula 1, formula 2 and formula 3 respectively:
[formula 1]
(wherein, R
1and R
2be substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C3 to C6 cycloalkyl, substituted or unsubstituted C6 to C12 aryl or halogen independently of one another, and a and b is the integer from 0 to 4 independently of one another);
[formula 2]
(wherein, R
1and R
2be substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C3 to C6 cycloalkyl, substituted or unsubstituted C6 to C12 aryl or halogen independently of one another, and a and b is the integer from 0 to 4 independently of one another); And
[formula 3]
(wherein, Q is substituted or unsubstituted C5 to C10 cycloalkyl, and a and b is the integer from 0 to 4 independently of one another).
In one embodiment, polycarbonate can have the mol ratio of the formula 1 (M1) of about 30 to 90mol%:5 to 30mol%:5 to 40mol%, formula 2 (M2) and formula 3 (M3).
In another embodiment, polycarbonate can have the mol ratio of the formula 1 (M1) of about 75 to 90mol%:5 to 15mol%:5 to 15mol%, formula 2 (M2) and formula 3 (M3).
In another embodiment, polycarbonate can have the mol ratio of the formula 1 (M1) of about 30 to 80mol%:10 to 30mol%:10 to 40mol%, formula 2 (M2) and formula 3 (M3).
In one embodiment, polycarbonate can have the mol ratio of formula 1 (M1), formula 2 (M2) and the formula 3 (M3) met the following conditions:
M1>M2+M3
M2≤M3
(wherein, M1 is the mol ratio of formula 1, and M2 is the mol ratio of formula 2, and M3 is the mol ratio of formula 3).
In one embodiment, polycarbonate can have the second-order transition temperature of about 135 DEG C to about 160 DEG C, the specific refractory power of about 1.58 to about 1.59 and according to ASTMD256 at room temperature 1/8 " Notched Izod Impact Strength of about 65kgcm/cm to about 95kgcm/cm that thick sample is measured.
In another embodiment, polycarbonate can have according to ASTMD542 at-30 DEG C 1/8 " Notched Izod Impact Strength of about 55kgcm/cm to about 85kgcm/cm that thick sample is measured.
Polycarbonate can comprise the sulfoacid compound represented by formula 4:
[formula 4]
(wherein, R9 is substituted or unsubstituted C1 to C20 alkyl, and R10 is substituted or unsubstituted C11 to C20 alkylidene group, and n is the integer from 0 to 5).
Another aspect of the present invention relates to a kind of method preparing polycarbonate.The method comprises the transesterify by the glycol that represented by formula 1-1, formula 2-1 and formula 3-1 and diaryl carbonate:
[formula 1-1]
(wherein, R
1and R
2be substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C3 to C6 cycloalkyl, substituted or unsubstituted C6 to C12 aryl or halogen independently of one another, and a and b is the integer from 0 to 4 independently of one another);
[formula 2-1]
(wherein, R
1and R
2be substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C3 to C6 cycloalkyl, substituted or unsubstituted C6 to C12 aryl or halogen independently of one another, and a and b is the integer from 0 to 4 independently of one another); And
[formula 3-1]
(wherein, Q is substituted or unsubstituted C5 to C10 cycloalkyl, and a and b is the integer from 0 to 4 independently of one another).
In one embodiment, the mol ratio of formula 1-1, formula 2-1 and formula 3-1 can be about 30 to 90mol%:5 to 30mol%:5 to 40mol%.
Beneficial effect
The invention provides polycarbonate with excellent chemical resistant properties, mobility, the transparency, room temperature/low temperature impact strength and thermotolerance and not deteriorated shock resistance and preparation method thereof.
Best mode
Polycarbonate according to an illustrative embodiment of the invention can be prepared by the transesterify of the glycol that represented by formula 1-1, formula 2-1 and formula 3-1 and diaryl carbonate.
[formula 1-1]
(wherein, R
1and R
2be substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C3 to C6 cycloalkyl, substituted or unsubstituted C6 to C12 aryl or halogen atom independently of one another, and a and b is the integer from 0 to 4 independently of one another).
[formula 2-1]
(wherein, R
1and R
2be substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C3 to C6 cycloalkyl, substituted or unsubstituted C6 to C12 aryl or halogen independently of one another, and a and b is the integer from 0 to 4 independently of one another).
[formula 3-1]
(wherein, Q is substituted or unsubstituted C5 to C10 cycloalkyl, and a and b is the integer from 0 to 4 independently of one another).
The example of formula 1-1 can comprise 2,2-two-(4-hydroxyphenyl)-propane, 2,2-two-(3,5-dimethyl-4-hydroxyphenyl)-propane, 2,2-two-(3,5-di-isopropyl-4-hydroxyphenyl)-propane etc.Particularly, 2,2-pairs-(4-the hydroxyphenyl)-propane being also called dihydroxyphenyl propane can be used.
The example of formula 2-1 can comprise 4,4'-bis-phenol, 2,2'-dimethyl-4,4'-'-biphenyl diphenols, 3,3-dimethyl-4,4-dihydroxybiphenyls, 2,2', 6,6'-tetramethyl--4,4'-bis-phenols etc.Particularly, 4,4'-bis-phenol can be used.
The example of formula 3-1 can comprise 1,2-ring pentanediol, 1,3-ring pentanediol, 1,2-cyclohexanediol, 1,3-cyclohexanediol, Isosorbide-5-Nitrae-cyclohexanediol, 1,2-cyclohexanedimethanol, 1,3-CHDM, 1,4 cyclohexane dimethanol, 1,2-ring heptanediol, 1,3-ring heptanediol, Isosorbide-5-Nitrae-ring heptanediol, 1,2-ring ethohexadiol, 1,3-ring ethohexadiol, Isosorbide-5-Nitrae-ring ethohexadiol etc.Particularly, 1,4 cyclohexane dimethanol can be used.
In one embodiment, the mol ratio of formula 1-1, formula 2-1 and formula 3-1 can be about 30 to 90mol%:5 to 30mol%:5 to 40mol%.When the mol ratio of formula 1-1, formula 2-1 and formula 3-1 is within the scope of this, polycarbonate can have the balance of the physicals comprising shock strength, chemical resistant properties and mobility.
The example of diaryl carbonate can comprise tolyl ester between dipheryl carbonate base ester, carboxylol ester, carbonic acid two (chloro-phenyl-) ester, carbonic acid, carbonic acid dinaphthyl ester, two (phenylbenzene) ester of carbonic acid (two (xenyl) ester of carbonic acid), diethyl carbonate, methylcarbonate, dibutyl carbonate, dicyclohexyl carbonate etc., but is not limited thereto.These diaryl carbonates can be used alone or use as mixture.Among those, dipheryl carbonate base ester is preferred.
In one embodiment, can add with the glycol of formula 1-1, formula 2-1 and formula 3-1 in diaryl carbonate with about 0.6 to about 1.0, the preferably mol ratio of about 0.7 to about 0.9.When carrying out the glycol of adding type 1-1, formula 2-1 and formula 3-1 with the mol ratio within the scope of this, excellent physical strength can be obtained.
In one embodiment, can under pressure-lowering condition, at about 150 DEG C to about 300 DEG C, preferably about 160 DEG C to about 280 DEG C, and more preferably from about carry out transesterify at 190 DEG C to about 260 DEG C.When temperature is within the scope of this, speed of reaction can be suitable and can reduce side reaction.
In addition, can in about 100 holders or lower, such as about 75 holders or lower, preferably about 30 holders or lower, and more preferably from about carry out transesterify at least about more than 10 minutes, preferably about 15 minutes to about 24 hours under 1 holder or lower pressure-lowering condition, and more preferably from about 15 minutes to about 12 hours.When pressure and time are within the scope of these, speed of reaction can be suitable and can reduce side reaction.
In one embodiment, can carry out reacting about 2 to about 9 hours to prepare polycarbonate resin at the temperature of about 160 DEG C to about 260 DEG C.
Can when there is alkali and alkaline-earth metal carries out transesterify as when catalyzer.The example of alkali and alkaline-earth metal can comprise LiOH, NaOH, KOH, but is not limited thereto.These metals can be used alone or use as mixture.The amount of catalyzer can be determined based on the amount of aromatic dihydroxy compound.In one embodiment, based on the aromatic dihydroxy compound of 1mol, catalyzer can with about 1 × 10
-8mol is to about 1 × 10
-3the amount of mol exists.When catalyzer uses with the amount within the scope of this, can obtain fully reactive and can minimize the generation of the by product caused by side reaction, this can improve thermostability and colour stability.
Or can be added in the polycarbonate produced by above-mentioned reaction with its mixture by the sulfonate compound represented by formula 4, it can remove the remaining activity of catalyzer.
[formula 4]
(wherein, R9 is substituted or unsubstituted C1 to C20 alkyl, and R10 is substituted or unsubstituted C11 to C20 alkylidene group, and n is the integer from 0 to 5).
The example of the sulfonate compound of formula 4 can comprise dodecyl p-toluenesulfonic esters, octadecyl p-toluenesulfonic esters, dodecyl DBS, octadecyl octadecyl benzenesulfonic acid ester etc.
In one embodiment, based on the monomer of 100 weight parts, sulfonate compound with about 0.0001 to about 0.001 weight part, preferably can exist with the amount of about 0.0003 to about 0.0008 weight part.When sulfonate compound exists with the amount within the scope of this, excellent thermostability and resistance to hydrolysis can be obtained.
In one embodiment, prepare final polycarbonate by reaction in－situ, wherein sulfonate compound is directly added to the polycarbonate obtained from this reaction.Alternatively, the polycarbonate obtained by transesterify can mix with sulfonate compound in extrusion.In this embodiment, the polycarbonate produced by this reaction can be transferred in forcing machine and can sulfonate compound be added in extrusion machine, then mixture being extruded into particle.
When adding sulfonate compound, can add together and extruding general additive.Additive can comprise fire retardant, antiseptic-germicide, demoulding system, thermo-stabilizer, antioxidant, photostabilizer, expanding material, dyestuff, inorganic additives, filler, softening agent, impact modifier, admixture, tinting material, stablizer, slipping agent, static inhibitor, pigment, weather agent and UV blocker, but is not limited thereto.These additives can separately or with it two or more combinationally use.
The polycarbonate prepared thus can comprise the repeating unit represented by formula 1, formula 2 and formula 3 respectively:
[formula 1]
(wherein, R
1and R
2be substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C3 to C6 cycloalkyl, substituted or unsubstituted C6 to C12 aryl or halogen independently of one another, and a and b is the integer from 0 to 4 independently of one another).
[formula 2]
(wherein, R
1and R
2be substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C3 to C6 cycloalkyl, substituted or unsubstituted C6 to C12 aryl or halogen independently of one another, and a and b is the integer from 0 to 4 independently of one another).
[formula 3]
(wherein, Q is substituted or unsubstituted C5 to C10 cycloalkyl, and a and b is the integer from 0 to 4 independently of one another).
In one embodiment, polycarbonate can have the mol ratio of the formula 1 (M1) of M1:M2:M3=about 30 to 90mol%:5 to 30mol%:5 to 40mol%, formula 2 (M2) and formula 3 (M3).
In another embodiment, polycarbonate can have the mol ratio of the formula 1 (M1) of M1:M2:M3=about 75 to 90mol%:5 to 15mol%:5 to 15mol%, formula 2 (M2) and formula 3 (M3).When being included in the mol ratio of the unit of the formula 1 (M1) within the scope of this, formula 2 (M2) and formula 3 (M3) when polycarbonate, polycarbonate can show excellent mobility, shock strength and chemical resistant properties, and especially can obtain the shock strength under excellent thermotolerance and room temperature.In addition, polycarbonate can guarantee low-refraction, obtain thus excellent when and it mixes time and the consistency of other resins.In the exemplary embodiment, polycarbonate can have the second-order transition temperature of 135 DEG C to about 160 DEG C, the specific refractory power of about 1.58 to about 1.59 and according to ASTMD256 at room temperature 1/8 " Notched Izod Impact Strength of about 65kgcm/cm to about 95kgcm/cm that thick sample is measured.
In another embodiment, polycarbonate can have the mol ratio of the formula 1 (M1) of M1:M2:M3=about 30 to 80mol%:10 to 30mol%:10 to 40mol%, formula 2 (M2) and formula 3 (M3).When being included in the mol ratio of the unit of the formula 1 (M1) within the scope of this, formula 2 (M2) and formula 3 (M3) when polycarbonate, polycarbonate can show excellent mobility, shock strength and chemical resistant properties, and the shock strength that especially can obtain under excellent actual flow, low temperature and chemical resistant properties.In the exemplary embodiment, polycarbonate have according to ASTMD542 at-30 DEG C 1/8 " Notched Izod Impact Strength of about 55kgcm/cm to about 85kgcm/cm that thick sample is measured.
In one embodiment, polycarbonate can have the mol ratio of formula 1 (M1), formula 2 (M2) and the formula 3 (M3) met the following conditions:
M1≥M2
M2≤M3
(wherein, M1 is the mol ratio of formula 1, and M2 is the mol ratio of formula 2, and M3 is the mol ratio of formula 3).
M1>M2 is preferred, and M1>M2+M3 is preferred.In this case, the shock strength under thermotolerance and room temperature can be excellent especially.
The mol ratio of M2 and M3 can be about 1:1 to 1:2.When the mol ratio of M2 and M3 is within the scope of this, excellent chemical resistant properties can be obtained.
Polycarbonate resin prepared in accordance with the present invention can have excellent chemical resistant properties, mobility and shock strength, and therefore may be used in various product.Such as, polycarbonate resin may be used for automobile, machine parts, Electrical and Electronic element, the office machinery comprising computer or groceries.Particularly, polycarbonate resin can not only for the housing of the such as Electrical and Electronic product of TV, computer, printer, washing machine, cassette phonograph, stereophonic sound system, mobile telephone, game console and toy, but also for humidifier, steam vacuum cleaner, vapour iron etc.
Can use suitable molding technique, such as extrusion molding, injection-molded, vacuum moulding, mold, blowing and calendering formation, be formed as product by polycarbonate resin.These methods are well-known for those of ordinary skill in the art.
The present invention is illustrated in greater detail with reference to following examples.These embodiments only provide for illustration purposes, and can not be construed as by any way limiting the present invention.
Embodiment
Embodiment 1
2 of 4.05kg is added continuously in reactor, 4 of two (4-hydroxyphenyl) propane (dihydroxyphenyl propane or BPA) of 2-, 0.19kg, 1 of 4'-biphenyl (BP), 0.14kg, the dipheryl carbonate base ester of 4-cyclohexanedimethanol (CHDM), 4.35kg and the KOH (dihydroxyphenyl propane based on 1mol) of 150ppb, and use the oxygen in nitrogen removing reactor.Reactor is heated to 160 DEG C, is then heated to 190 DEG C, carry out reaction at such a temperature 6 hours.After 6 hours, reactor be heated to 210 DEG C and keep 1 hour under 100 holders.Reactor be heated to 260 DEG C and keep 1 hour under 20 holders, and be decompressed to 0.5 holder subsequently and keep 1 hour.Subsequently, the dodecyl p-toluenesulfonic esters of 0.0005phr, the octadecyl 3-(3 of 0.03phr is added in molten polymer, 5-bis--uncle-4-hydroxyphenyl) three (2,4-, bis--tert-butyl phenyl) phosphoric acid ester of propionic ester and 0.05phr mixing about 10 minutes to be to form uniform mixture.
Embodiment 2
2 of 3.83kg is added continuously in reactor, 4 of two (4-hydroxyphenyl) propane (dihydroxyphenyl propane) of 2-, 0.19kg, 1 of 4'-biphenyl, 0.28kg, the dipheryl carbonate base ester of 4-cyclohexanedimethanol, 4.35kg and the KOH (dihydroxyphenyl propane based on 1mol) of 150ppb, and use the oxygen in nitrogen removing reactor.Then, polyreaction is carried out in the same manner as in example 1.
Embodiment 3
2 of 3.60kg is added continuously in reactor, 4 of two (4-hydroxyphenyl) propane (dihydroxyphenyl propane) of 2-, 0.37kg, 1 of 4'-biphenyl, 0.28kg, the dipheryl carbonate base ester of 4-cyclohexanedimethanol, 4.35kg and the KOH (dihydroxyphenyl propane based on 1mol) of 150ppb, and use the oxygen in nitrogen removing reactor.Then, polyreaction is carried out in the same manner as in example 1.
Embodiment 4
2 of 3.15kg is added continuously in reactor, 4 of two (4-hydroxyphenyl) propane (dihydroxyphenyl propane) of 2-, 0.37kg, 1 of 4'-biphenyl (BP), 0.57kg, the dipheryl carbonate base ester of 4-cyclohexanedimethanol, 4.35kg and the KOH (dihydroxyphenyl propane based on 1mol) of 150ppb, and use the oxygen in nitrogen removing reactor.Then, polyreaction is carried out in the same manner as in example 1.
Embodiment 5
2 of 2.25kg is added continuously in reactor, 4 of two (4-hydroxyphenyl) propane (dihydroxyphenyl propane) of 2-, 0.74kg, 1 of 4'-biphenyl, 0.85kg, the dipheryl carbonate base ester of 4-cyclohexanedimethanol, 4.35kg and the KOH (dihydroxyphenyl propane based on 1mol) of 150ppb, and use the oxygen in nitrogen removing reactor.Then, polyreaction is carried out in the same manner as in example 1.
Embodiment 6
2 of 1.35kg is added continuously in reactor, 4 of two (4-hydroxyphenyl) propane (dihydroxyphenyl propane) of 2-, 1.11kg, 1 of 4'-biphenyl, 0.85kg, the dipheryl carbonate base ester of 4-cyclohexanedimethanol, 1.13kg and the KOH (dihydroxyphenyl propane based on 1mol) of 150ppb, and use the oxygen in nitrogen removing reactor.Then, polyreaction is carried out in the same manner as in example 1.
Comparative example 1
2 of 4.5kg is added continuously in reactor, 2-two (4-hydroxyphenyl) propane (dihydroxyphenyl propane), the dipheryl carbonate base ester of 4.35kg and the KOH (dihydroxyphenyl propane based on 1mol) of 100ppb, and use the oxygen in nitrogen removing reactor.Reactor is heated to 160 DEG C, is then heated to 190 DEG C, carry out reaction at such a temperature 6 hours.After 6 hours, reactor be heated to 220 DEG C and keep 1 hour under 70 holders.Reactor be heated to 260 DEG C and keep 1 hour under 20 holders, and be decompressed to 0.5 holder subsequently and keep 1 hour.Subsequently, the dodecyl p-toluenesulfonic esters of 0.0005phr, the octadecyl 3-(3 of 0.03phr is added in molten polymer, 5-bis--uncle-4-hydroxyphenyl) three (2,4-, bis--tert-butyl phenyl) phosphoric acid ester of propionic ester and 0.05phr mixing about 10 minutes to be to form uniform mixture.
Comparative example 2
2 of 3.83kg is added continuously in reactor, 4 of two (4-hydroxyphenyl) propane (dihydroxyphenyl propane) of 2-, 0.56kg, the dipheryl carbonate base ester of 4'-biphenyl, 4.35kg and the KOH (dihydroxyphenyl propane based on 1mol) of 100ppb, and use the oxygen in nitrogen removing reactor.Then, polyreaction is carried out in the mode identical with comparative example 1.
Comparative example 3
2 of 3.15kg is added continuously in reactor, 4 of two (4-hydroxyphenyl) propane (dihydroxyphenyl propane) of 2-, 1.11kg, the dipheryl carbonate base ester of 4'-biphenyl, 4.35kg and the KOH (dihydroxyphenyl propane based on 1mol) of 150ppb, and use the oxygen in nitrogen removing reactor.Then, polyreaction is carried out in the mode identical with comparative example 1.
Comparative example 4
2 of 4.05kg is added continuously in reactor, 4 of two (4-hydroxyphenyl) propane (dihydroxyphenyl propane) of 2-, 0.28kg, the dipheryl carbonate base ester of 4'-biphenyl, 4.35kg and the KOH (dihydroxyphenyl propane based on 1mol) of 150ppb, and use the oxygen in nitrogen removing reactor.Then, polyreaction is carried out in the same manner as in example 1.
Comparative example 5
2 of 3.15kg is added continuously in reactor, 1 of two (4-hydroxyphenyl) propane (dihydroxyphenyl propane) of 2-, 0.85kg, the dipheryl carbonate base ester of 4-cyclohexanedimethanol, 4.35kg and the KOH (dihydroxyphenyl propane based on 1mol) of 150ppb, and use the oxygen in nitrogen removing reactor.Then, polyreaction is carried out in the same manner as in example 1.
Table 1
At 270 DEG C, use biaxial extruder (L/D=36, Φ=32) to be extruded by the polycarbonate resin prepared in embodiment and comparative example, and use nodulizer to form it into particle.The physicals of the particle of following assessment preparation, and in table 2 result is shown.
The evaluation method of physicals
(1) melt index (MI, g/10min)
Flow index tester (model: F-W01, Toyoseiki manufacture) is used to measure melt index under 250 DEG C of loads with 10kg.
(2) second-order transition temperature (DEG C)
DSC (model: Q100, TAInstruments) is used to measure second-order transition temperature under the temperature increase rate of 10 DEG C/min.
(3) specific refractory power
Specific refractory power is measured according to ASTMD257.
(4) actual flow (cm)
Injector (DHC120WD, 120 tons, Dongshinen-TechCo., Ltd.) is used to measure actual flow distance (cm) of the particle at the thick spiral form of the 2mm of the die temperature lower mould of 290 DEG C and 80 DEG C.
(5) shock strength (kgcm/cm) at room temperature
Use injector (DHC120WD, 120 tons, Dongshinen-TechCo., Ltd.) under the die temperature of the molding temperatures of 270 DEG C and 70 DEG C, the granulated of preparation is become 1/8 " IZOD sample; then carry out assessing (1/8 ", breach) according to ASTMD256.
(6) shock strength (kgcm/cm) at low temperatures
According to ASTMD542,1/8 at-30 DEG C " IZOD sample is measured shock strength at low temperatures.
(7) chemical resistant properties
* to the chemical resistant properties of alcohols: prepare the drawn samples according to ASTMD638 by injection molding, afterwards, according to ASTMD543, the strain of 2.1% is applied for assessment environmental stress crack resistance to sample, and methyl alcohol and Virahol are dripped thereon.After 10 minutes, the crackle that curved part produces is observed.(◎: flawless, zero: minute crack, △: many crackles, X: crackle shrouds (hazeofcracks))
* the transmissivity after being positioned in coating solution: 2.5mm flat sample to be placed in the coating diluent (main component: methyl iso-butyl ketone (MIBK), pimelinketone and cellosolvo) for polycarbonate resin 2 minutes and at 80 DEG C dry 30 minutes, turbidometer (Gmbh4725, BYK-Gardner) is used to measure visible light transmission rate (%) subsequently.
Table 2
In test process, the melt index (MI) of the polycarbonate according to embodiment 1 to 6 and comparative example 1 to 3 is adjusted to 30g/10min.Polycarbonate according to comparative example 4 and 5 has MI high immeasurably under 250 DEG C and 10kg load.According to the polycarbonate of embodiment 1 to 6, there is the mobility of excellence, shock strength, chemical resistant properties and the transmissivity under room temperature and low temperature.But, according to the chemical resistant properties that comparative example 1 only uses the polycarbonate performance of BPA obviously to reduce, and according to the polycarbonate of alicyclic diol that do not adopt of comparative example 2 and 3, there is shock strength under the room temperature of reduction and actual flow.Not using the polycarbonate of BP to have excellent actual flow but showing the shock strength under the room temperature and low temperature reduced according to comparative example 4 and 5.Particularly, there is according to the polycarbonate of comparative example 4 chemical resistant properties of deterioration equally.
Although disclosed some embodiments in this article, it should be understood that these embodiments provide by means of only the mode illustrated, and when not deviating from the spirit and scope of the present invention, can various amendment, change and change have been carried out.Therefore, scope of the present invention should only be limited by appended claims and equivalent thereof.
Claims (8)
1. polycarbonate, comprises the repeating unit represented by formula 1, formula 2 and formula 3 respectively:
[formula 1]
Wherein, R
1and R
2be substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C3 to C6 cycloalkyl, substituted or unsubstituted C6 to C12 aryl or halogen independently of one another, and a and b is the integer from 0 to 4 independently of one another;
[formula 2]
Wherein, R
1and R
2be substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C3 to C6 cycloalkyl, substituted or unsubstituted C6 to C12 aryl or halogen independently of one another, and a and b is the integer from 0 to 4 independently of one another; And
[formula 3]
Wherein, Q is substituted or unsubstituted C5 to C10 cycloalkyl, and a and b is the integer from 0 to 4 independently of one another,
Wherein, described polycarbonate has the mol ratio of the formula 1 (M1) of 30 to 90mol%:5 to 30mol%:5 to 40mol%, formula 2 (M2) and formula 3 (M3).
2. polycarbonate according to claim 1, wherein, described polycarbonate has the mol ratio of the formula 1 (M1) of 75 to 90mol%:5 to 15mol%:5 to 15mol%, formula 2 (M2) and formula 3 (M3).
3. polycarbonate according to claim 1, wherein, described polycarbonate has the mol ratio of the formula 1 (M1) of 30 to 80mol%:10 to 30mol%:10 to 40mol%, formula 2 (M2) and formula 3 (M3).
4. polycarbonate according to claim 1, wherein, described polycarbonate has the mol ratio of formula 1 (M1), formula 2 (M2) and the formula 3 (M3) met the following conditions:
M1>M2+M3
M2≤M3
Wherein, M1 is the mol ratio of formula 1, and M2 is the mol ratio of formula 2, and M3 is the mol ratio of formula 3.
5. polycarbonate according to claim 2, wherein, described polycarbonate have the second-order transition temperature of 135 to 160 DEG C, the specific refractory power of 1.58 to 1.59 and according to ASTMD256 at room temperature 1/8 " Notched Izod Impact Strength of 65 to 95kgcm/cm that thick sample is measured.
6. polycarbonate according to claim 3, wherein, described polycarbonate have according to ASTMD542 at-30 DEG C 1/8 " Notched Izod Impact Strength of 55 to 85kgcm/cm that thick sample is measured.
7. polycarbonate according to claim 1, wherein, described polycarbonate comprises the sulfoacid compound represented by formula 4:
[formula 4]
Wherein, R9 is substituted or unsubstituted C1 to C20 alkyl, and R10 is substituted or unsubstituted C11 to C20 alkylidene group, and n is the integer from 0 to 5.
8. prepare a method for polycarbonate, comprise the transesterify by the glycol that represented by formula 1-1, formula 2-1 and formula 3-1 and diaryl carbonate:
[formula 1-1]
Wherein, R
1and R
2be substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C3 to C6 cycloalkyl, substituted or unsubstituted C6 to C12 aryl or halogen independently of one another, and a and b is the integer from 0 to 4 independently of one another;
[formula 2-1]
Wherein, R
1and R
2be substituted or unsubstituted C1 to C6 alkyl, substituted or unsubstituted C3 to C6 cycloalkyl, substituted or unsubstituted C6 to C12 aryl or halogen independently of one another, and a and b is the integer from 0 to 4 independently of one another; And
[formula 3-1]
Wherein, Q is substituted or unsubstituted C5 to C10 cycloalkyl, and a and b is the integer from 0 to 4 independently of one another,
Wherein, the mol ratio of formula 1-1, formula 2-1 and formula 3-1 is 30 to 90mol%:5 to 30mol%:5 to 40mol%.
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| PCT/KR2011/009684 WO2013047955A1 (en) | 2011-09-30 | 2011-12-15 | Polycarbonate and method for preparing same |
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| KR101685245B1 (en) * | 2013-12-30 | 2016-12-09 | 롯데첨단소재(주) | Copolymerized polycarbonate resin, method for preparing the same and article comprising the same |
| KR101714834B1 (en) * | 2014-04-30 | 2017-03-10 | 롯데첨단소재(주) | Polycarbonate resin, method for preparing the same, and article comprising the same |
| KR102036891B1 (en) * | 2014-05-26 | 2019-10-25 | 삼성전자주식회사 | Polymer compositions and formed article and manufacturing method of the same |
| JP6976715B2 (en) * | 2017-05-23 | 2021-12-08 | 本州化学工業株式会社 | Aromatic polycarbonate oligomer solid |
| CN109825055B (en) * | 2019-01-15 | 2021-06-11 | 金发科技股份有限公司 | Polycarbonate composition and preparation method thereof |
| KR20210000860A (en) | 2019-06-26 | 2021-01-06 | 김경호 | Green tea |
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| EP2762516B1 (en) | 2016-10-12 |
| EP2762516A4 (en) | 2015-05-27 |
| US8410240B1 (en) | 2013-04-02 |
| KR101489952B1 (en) | 2015-02-04 |
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| WO2013047955A1 (en) | 2013-04-04 |
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